METHOD FOR FABRICATING QUANTUM DOT LIGHT EMITTING DIODES (LEDs) WITH SUPPRESSED PHOTOBRIGHTING

ABSTRACT

A device and associated method are provided for a light emitting diode device (LED) with suppressed quantum dot (QD) photobrightening. The QD surfaces, with a maximum cross-sectional dimension of 10 nanometers, are treated with a solution including a multi-valent cation salt. In response to heating the solution, multi-valent cations become attached to the surface of the QD nanocrystals, forming treated QDs that are deposited overlying a top surface of an LED. The LED device emits a non-varying intensity of first wavelength light in the visible spectrum from the treated QDs, when subjected to a continuous exposure of a second wavelength of LED light having an intensity of greater than 50 watts per square centimeter. For example, blue, green, or red color light may be emitted when exposed to LED light in the ultraviolet (UV) spectrum, or a green or red color light when exposed to a blue color LED light.

RELATED APPLICATIONS

Any and all applications, if any, for which a foreign or domesticpriority claim is identified in the Application Data Sheet of thepresent application are hereby incorporated by reference under 37 CFR1.57.

BACKGROUND OF THE INVENTION 1. Field of the Invention

This invention generally relates to quantum dot (QD) emissions and, moreparticularly, to a QD light emitting diode (LED) with suppressedphotobrightening.

2. Description of the Related Art

Quantum dots (QDs), or semiconducting nanocrystals are chemical objectswith a size falling between cluster molecules (aggregates of 5-10⁵atomic or molecular units) and bulk materials (nanometers (nm) to meters(m)). Since first being fabricated through molecular beam epitaxy, QDshave evoked interest as their band gap was found to be tunable with thesize of the structure. Decades later, a solution-based approach forfabrication of QDs through colloidal chemistry brought significantattention to these materials. Colloidal syntheses allowed for thepreparation of a material of any size and varied chemical composition,with almost any optical band gap. Further, the solution-based approachproved to a feasible route to scale up the preparation of QDs incommercially significant amounts. The control of the optical band gapled to the tunability of optical properties, such as emission andabsorbance. Such tunability of physical properties ultimately dictatedthe potential application of the QD materials, as the tunability ofabsorbance spectrum was found to be useful for solar cell applications,while the tunability of emission properties allowed these materials tobe utilized in the generation of light at specific wavelengths fordisplay and lighting applications.

Currently, there are two major strategies for incorporating QDs in lightemitting devices. The first strategy uses direct emitting LEDs, wherecharges are directly injected into QDs through the LED structure,leading to radiative recombination. In the second strategy, QDs areutilized as color conversion materials, as explained in more detailbelow.

FIGS. 1A and 1B depict LEDs utilizing different color conversiontechniques (prior art). FIG. 1A depicts a remote conversion techniquewhere the QDs are embedded in a film 100 and irradiated by blue orultraviolet (UV) LED 102, and where the LED is physically separated fromthe color converter. As shown, light is delivered to the colorconversion film via a waveguide 104 and reflector 106. FIG. 1B depictsthe second type of color conversion, where the QD embedded film 100 isplaced directly on LED 102, with or without a spacer (not shown).

The “directly on LED” approach of FIG. 1B permits the fabrication ofmore efficient emitting devices that require substantially less QDmaterial. However, despite these benefits, this approach has severaltechnological challenges. These challenges include: high operatingtemperatures (often above 100° C.) due to proximity to the lightemitting LED, high photon flux, and the tight packing of the QDmaterials due to miniaturization. These factors generally lead toemission quenching through different mechanisms, which reducesconversion efficiency. Much of the research in this field is aimed ataddressing quenching mechanisms and determining pathways to minimize theimpact of such factors. Generally, the strategies of coating the QDcores with large (also known as “giant” (5-10 nm) shell or multipleshells are utilized for the improvement of the emission properties andeliminating of emission quenching mechanisms. However, other factors arepresent that often affect the emissive properties of QDs exposed todirect LED emissions. One such issue is photobrightening—a process whereQD emission increases under the conditions of a high steady state(constant) photon flux. While it might be initially assumed that thephotobrightening effect would be beneficial due to the increasedbrightness of the emissive device, such changes in the emissiveproperties are often unacceptable in commercial products because theydisrupt the color gamut of a display and change the color temperature ofthe lighting system.

At the time of this writing, the physical mechanisms underlyingphotobrightening are poorly understood and are not well addressed in thescientific literature. However, the effect of photobrightening cannot beneglected in the fabrication of practical emissive devices. The majorityof the published photobrightening research covers short-term pulsedirradiation (with a range of pulse times), which is not directlyapplicable to LED applications where the QDs are subjected to 50-500W/cm² continuous light for extended periods of time (i.e., hours ofillumination). With the directly on LED configuration, such as shown inFIG. 1B, the integrated emission intensity of quantum dots may increaseas much as 20-30% over the course of 60 minutes of operation. Moreover,the photobrightening effect may well be size dependent, which is rathercommon for nanostructured materials. For example, more pronouncedphotobrightening may occur for smaller nanoparticles. While being easierto make, the smaller nanoparticles (core or single shell particles) arenot utilized for color converting applications as they are alsosensitive to various degradation/decomposition and emission quenchingeffects. As mentioned above, the growth of multi-shell structures or“giant” shell growth is utilized to suppress these effects, often makingparticles of the size greater than 10 nm. Further, photobrightening maybe present for nanop articles emissions in both the visible, and outsidethe visible ranges of the electromagnetic spectrum. Within the contextof display and lighting applications, the visible range is of particularinterest, where the QD material systems are typically cadmium and zincchalcogenides (as well as their alloys), ternary chalcogenides (e.g.,copper indium sulfide and similar materials), and indium phosphide.

FIG. 2 is a graph depicting changes in LED emission intensity as aresult of photobrightening. Curve 200 represents the initial emission ofa directly on LED QD device after thermal equilibration. Curve 202represents the emission after 1 hour of the LED operating at full power.Generally, the photobrightening effect may be small for larger(red-emitting) nanoparticles, while for green (and potentially blue)emitters, the photobrightening effect is more pronounced. That is, thecolor emitted by a QD is dependent upon the particle size and particlecomposition. Green and blue emitting QDs may be smaller than redemitters due to a dependence between size and band gap, and as such,blue and green QDs are typically more susceptible to thephotobrightening effect. Since the human eye is most sensitive to thecolor green, changes in green emission intensity are the most criticalin the design of the color gamut and color temperature for display andlighting application.

Currently, the QDs utilized for directly on LED color conversion (FIG.1B) usually utilize a multi-shell structure, where several shells ofdifferent semiconducting materials are grown around the core, or “giant”structure, where the thickness of the shell is comparable with the QDsize (up to 5 nm). These materials, while often less prone tophotobrightening, generally require multi-step preparation procedures atelevated temperatures, which makes these materials less competitive dueto high manufacturing costs. Further, photobrightening is not addressedin the “giant”/multi-shell technical literature, which is most likelydue to the structural complexity of these types of QDs.

It would be advantageous if the effect of QD photobrightening could besuppressed without forming multiple layers of shell material, or withoutforming a “giant” shell that is a thick as the core particle.

SUMMARY OF THE INVENTION

Disclosed herein is a method of modifying quantum dots (QDs) to suppressthe effect of photobrightening for “directly on light emitting diode(LED)” applications, when the QDs are subjected to constant high photonflux. In one aspect, the surface of the quantum dots is modified throughexposure to divalent cation salts to replace some of the surface atomsand/or block the pre-existing surface sites that may contribute to thephotobrightening effect. Such “surface doping” results in almostcomplete suppression of photobrightening. In one example provided below,the changes of emission intensity over 80 minutes of constant LEDoperation were diminished from 18-19% to 5%.

Accordingly, methods are provided for quantum dot photobrighteningsuppression and for forming a light emitting diode device withsuppressed quantum dot photobrightening. The methods provide QDnanocrystals having a surface, with a maximum cross-sectional dimensionof 10 nanometers (nm), capable of emissions in the visible spectrum oflight. The QD nanocrystal surfaces are treated with a solution includinga multi-valent cation salt, with the solution being heated to atemperature in the range of 50 to 200 degrees C. In response to heatingthe solution, multi-valent cations become attached to the surface of thequantum dot nanocrystals, forming treated QDs with suppressedphotobrightening. In one aspect, the multi-valent cations becomeattached to the QD nanocrystal surfaces through solution-basedpseudo-atomic layer deposition.

The treated QDs are deposited overlying a top surface of a lightemitting diode (LED). The result is an LED device capable of emitting anon-varying intensity of a first wavelength light in the visiblespectrum from the treated QDs, when subjected to a continuous exposureof a second wavelength of LED light having an intensity of greater than50 watts per square centimeter (W/cm²). In one aspect, the treated QDsare mixed with an epoxy, silicon, or acrylate based polymer matrixmaterials to form a matrix paste, and the matrix paste is deposited onthe LED.

For example, the LED device may include treated QDs emitting anon-varying intensity of blue, green, or red color light when exposed toLED light in the ultraviolet (UV) spectrum. In another example, the LEDdevice may include the treated QDs emitting a non-varying intensity ofgreen or red color light when exposed to a blue color LED light.

Typically, the QD nanocrystals have either a solitary core orcore-single shell structure. In the case of a solitary core, the coresurface is the QD nanocrystal surface. In the case of a core-singleshell structure, the shell comprises the QD nanocrystal surface. Theinterface between the core and shell may, or may not be alloyed. If QDnanocrystal surface is a binary or binary alloyed material, then the QDnanocrystals are treated with a solution including divalent cationsalts. For example, the QD nanocrystal surface may be: CdS, CdSe, CdTe,GaAs, InAs, InN, InP, ZnS, ZnSe, ZnTe, or combinations thereof. If theQD nanocrystal surface is a tertiary or tertiary alloyed material, theQD nanocrystals are treated with trivalent cation salts, divalent cationsalts, monovalent cation salts, or combinations thereof. For example,the QD nanocrystal surface may be: ZnSSe, ZnSeTe, ZnSTe, CdSSe, CdSeTe,CdSTe, ZnCdS, ZnCdSe, ZnCdTe, ZnCdSSe, ZnCdSeTe, InGaAs, GaAlAs, InGaN,CuInS₂, CuGaS₂, Cu(In,Ga)Se₂, Cu(Zn,Sn)Se₂, Cu(Zn,Sn)S₂, Culn(Se,S)₂,CuZn(Se,S)₂, CuSn(Se,S)₂, Cu(Zn,Sn)(Se,S)₂, or combinations thereof.

In one aspect, the QD nanocrystal surface is a Type III-V semiconductorQD, and the QD nanocrystal surfaces are treated with a solutionincluding trivalent cation salts, divalent cation salts, or combinationsthereof. The trivalent cation salts may be comprised of Al, Ga, In, Fe,Sb, or Bi.

Additional details of the above-described methods, treated quantum dotswith suppressed photobrightening, and an associated LED device areprovided below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B depict LEDs utilizing different color conversiontechniques (prior art).

FIG. 2 is a graph depicting changes in LED emission intensity as aresult of photobrightening.

FIGS. 3A and 3B are partial cross-sectional views depicting treatedquantum dots (QDs) with suppressed photobrightening.

FIG. 4 is a partial cross-sectional view depicting an exemplary QD lightemitting diode (LED) device with suppressed photobrightening.

FIG. 5 depicts the evolution of emission intensity upon continuousirradiation as an illustration of the photobrightening effect on theuntreated green-emitting QDs placed in a matrix material on top of anLED.

FIGS. 6A and 6B are partial cross-sectional views representing the QDnanocrystal surface treatment.

FIG. 7 is a graph depicting the performance of QDs before and after asurface treatment (at two different temperatures) with QDs depositeddirectly upon a blue light emitting LED.

FIG. 8 is a flowchart illustrating a method for suppressing quantum dotphotobrightening.

FIG. 9 is a flowchart illustrating a method for forming a light emittingdiode device with suppressed quantum dot photobrightening.

DETAILED DESCRIPTION

FIGS. 3A and 3B are partial cross-sectional views depicting treatedquantum dots (QDs) with suppressed photobrightening. The treated QD 300comprises a QD nanocrystal 302 having a surface 304 with a maximumcross-sectional dimension 306 of 10 nanometers (nm), capable ofemissions in the visible spectrum of light. The size of the QDnanostructures is mentioned as a means of distinguishing these QDs fromlarger sized QDs made from multiple shells, or “giant” QDs formed fromone extremely thick shell. Cations 308 are attached to the surface 304of the QD nanocrystal 302. A cation is a positively charged ion (atom).A typical cation has a radius of less than 0.8×10⁻¹⁰ meters. The treatedQD 300 emits a non-varying intensity of first wavelength of light in thevisible spectrum when subjected to a continuous exposure of a secondwavelength of light having an intensity of greater than 50 watts persquare centimeter (W/cm²). The exact intensity limits are dependent uponthe QD material and the wavelength of the light to which the QDs areexposed. In one aspect, the treated quantum dots 300 emit a blue, green,or red color light when exposed to light in the ultraviolet (UV)spectrum. In another aspect, the treated quantum dots emit a green orred color light when exposed to a blue color light. As used herein, anon-varying intensity of light is defined as a change of 5% or less.

As shown in FIG. 3A, the QD nanocrystal 302 may have the structure of asolitary core, or as shown in FIG. 3B, the QD nanocrystal 302 may have acore-single shell structure. That is, the combination of core 302 a andshell 302 b comprise QD nanocrystal 302. In the case of the core-singleshell structure, the QD nanocrystal surface 304 is the surface of theshell. In some aspects not explicitly shown, the structure of thetreated quantum dot 300 may have more than one shell comprised ofdifferent materials. In another aspect not shown, the core 302 a andshell 302 b may be anisotropic with the aspect ratio in the range of1-2, in which case the core is not spherical. Although generallydepicted as spherical, the treated QD and QD nanocrystal core are notlimited to any particular shape. In another aspect not shown, an alloymay be formed between the core and shell and (or) between the shells.

If the QD nanocrystal surface 304 is a binary or binary alloyedmaterial, then the cations 308 are divalent cations. Some examples ofdivalent cations include Zn, Cd, Hg, and Pb. However, the treated QDsare not limited to any particular divalent cation. A divalent cation hasa charge of +2. Binary refers to a material or molecule comprised of twoelements. Binary alloyed refers to an alloy of two or more binarymaterials. Generally, alloys are understood to be a mixture of a metalwith another element. For example, the QD nanocrystal surface 304 maybe: CdS, CdSe, CdTe, GaAs, InAs, InN, InP, ZnS, ZnSe, ZnTe, orcombinations thereof. However, the QD surfaces are not necessary limitedto these examples of binary or binary alloyed materials.

If the QD nanocrystal surface 304 is a tertiary or tertiary alloyedmaterial, the cations 308 may be trivalent cations, divalent cations,monovalent cations, or combinations thereof. A trivalent cation has acharge of +3 and a monovalent cation has a charge of +1. Trinary refersto a material or molecule comprised of three elements, and trinaryalloyed refers to an alloy of two or more trinary materials. Forexample, the QD nanocrystal surface 304 may be: ZnSSe, ZnSeTe, ZnSTe,CdSSe, CdSeTe, CdSTe, ZnCdS, ZnCdSe, ZnCdTe, ZnCdSSe, ZnCdSeTe, InGaAs,GaAlAs, InGaN, CuInS2, CuGaS2, Cu(In,Ga)Se2, Cu(Zn,Sn)Se₂, Cu(Zn,Sn)S₂,CuIn(Se,S)₂, CuZn(Se,S)₂, CuSn(Se,S)₂, Cu(Zn,Sn)(Se,S)₂, or combinationsthereof. However, the QD surfaces are not necessary limited to theseexamples of trinary or trinary alloyed materials.

In one aspect, the QD nanocrystal surface 304 is a Type III-Vsemiconductor QD, and the cations 308 may be trivalent cations, divalentcations, or a combination of both. The trivalent cations may, forexample, be Al, Ga, In, Fe, Sb, or Bi. Other trivalent cations, besidesthe ones listed above, may also be used. Alternatively, photobrighteningmight be suppressed with treatments with chalcodenide precursors,however, as it is known from the literature, the enrichment of the QDsurface with chalcogen atoms may negatively affect the emissionproperties of QDs. It should also be noted that the cations in saltsused to treat the QD surfaces need not necessary be the same metalmaking up the QD nanocrystal surface material.

FIG. 4 is a partial cross-sectional view depicting an exemplary QD lightemitting diode (LED) device with suppressed photobrightening. The device400 comprises an LED 402 with a top surface 404. A plurality of treatedQDs 300 with suppressed photobrightening overlies the LED top surface404. As explained above, each treated QD comprises a QD nanocrystal,capable of emissions in the visible spectrum of light, and having asurface with a maximum cross-sectional dimension of 10 nm. Cations areattached to the surface of the QD nanocrystals (see FIGS. 3A and 3B).Details of the treated QDs 300 have been presented above and are notrepeated here in the interest of brevity.

The device 400 emits a non-varying intensity of first wavelength oflight from the treated QDs 300 in the visible spectrum when subjected toa continuous exposure of a second wavelength of LED light having anintensity of greater than 50 W/cm². In one aspect, the device 400 emitsa blue, green, or red color light from the treated QDs when exposed toLED light in the UV spectrum. In another aspect, the device 400 emits agreen or red color light from the treated QDs when exposed to a bluecolor LED light.

In one aspect as shown, an epoxy, silicon, or acrylate based polymermatrix material 406 overlies the top surface of the LED, and the treatedQDs 300 are embedded in the matrix material. Alternatively but notshown, the treated QDs may be deposited on the LED top surface withoutthe use of a matrix material. That is, the treated QDs are spatiallyseparated from the LED by a non-emissive material. As shown, electrodes408 and 410 extend from the LED bottom surface 412, however, the device400 is not limited to any particular electrical interface configurationor LED shape.

FIG. 5 depicts the evolution of emission intensity upon continuousirradiation as an illustration of the photobrightening effect on theuntreated green-emitting QDs placed in a matrix material on top of anLED. When applied directly on an LED or micro LED, green emitting QDssuffer from photobrightening with an extreme example of such effectillustrated in the figure. In this case photobrightening causes anemission growth up to almost 40% as compared to the thermallyequilibrated value. The initial point of the measurement (time=0) wasrecorded after thermal equilibrium in the emitting layer had beenachieved to eliminate competing thermal processes.

FIGS. 6A and 6B are partial cross-sectional views representing the QDnanocrystal surface treatment (the surface ligands are omitted forclarity). The surface ligands are charged, or neutral moleculeschemically attached to the surface of the QD. Such ligands mightoriginate from the colloidal synthesis of the QD nanocrystals or theycan be added in subsequent treatments. The ligands are utilized tocontrol the growth of the nanop articles during synthesis and later theyare used to prevent the aggregation of the particles. In one example,the green emitting QD nanocrystals, with a peak emission at about 530nm, were comprised of alloyed Cd_(x)Zn_(1-x)Se core 302 a and a ZnSshell 302 b, synthesized through a scalable single-step synthesis of asingle shell formed around a core, providing a particle size of around 6nm. The ability to suppress photobrightening in QD nanocrystals, asdescribed herein, makes the simple one-step synthesis process anadvantageous fabrication process, when compared to the several stepsrequired to make the conventional multi-shell or giant shell structuresmentioned in the Background Section, above. Further, the ability tosuppress photobrightening in solitary core structure QD nanocrystals iseven more advantageous.

In order to suppress changes in emission intensity, the green-emittingalloyed QD nanocrystals were treated with zinc oleate in 1-octadecene atelevated temperatures. This treatment was performed to deactivate activesites on the surface of QD nanocrystal, which may participate inphotobrightening. Such deactivation is done by pseudo-atomic layerdeposition of zinc atoms on the QD nanocrystal surface and/or potentialreplacement of the poorly attached surface atoms. Atomic layerdeposition (ALD) is based on the sequential use of a gas phase chemicalprocess. ALD is considered a subclass of chemical vapor deposition. Themajority of ALD reactions use two chemicals, typically calledprecursors. These precursors react with the surface of a material one ata time in a sequential, self-limiting, manner. Through the repeatedexposure to separate precursors, a thin film is slowly deposited. Asused herein, pseudo-ALD is a solution-based approach, in contrast to thegas phase approach of ALD. Also in contrast to ALD, pseudo-ALD uses onlya single precursor to deposit only one element, not two.

Alternatively, instead of zinc oleate, the QD nanocrystal surfacetreatment can be performed using any other divalent cations that arecapable of attachment to a QD nanocrystal structure. The results of thetreatment are schematically represented on the FIGS. 6A and 6B, wherespots labeled as 308 represent newly attached cations. This salttreatment may also be understood to be QD nanocrystal “surface” doping,where the doping atom replaces surface imperfections that originate fromthe single-step synthesis procedure. These imperfections are chemicallyunstable surface sites.

In one example, the treatment was performed by the addition of QDnanocrystals suspended in toluene into a solution of zinc oleate (200milligrams (mg)) in 2 milliliters (mL) of 1-octadecene. The mixture wasstirred at a temperature within the range of 100-150° C. for 1 hour.Generally, any solvent with high boiling point, capable of dispersing QDnanocrystals and solubilizing a metal salt can be utilized for suchmodification. Such solvents typically include saturated, non-saturated,branched, cyclic, and aromatic hydrocarbons with boiling point above thereaction temperature. Additionally, amines, esters and ethers withsaturated, non-saturated, branched, cyclic or aromatic hydrocarbonmoieties can be utilized for such a purpose.

Following the treatment of the QD nanocrystal surfaces, the treated QDscan be purified using well-known procedures by the addition of anon-solvent (generally polar solvents, such as alcohols, ketones,aldehydes, ethers, or esters), and separation of the precipitatedtreated QDs. The resulting materials can then be incorporated into anLED structure, by redispersion of the treated QDs in a matrix material,such as an epoxy-, silicone-, or acrylate-based polymer. In principle,any polymeric material capable of transmittance of emitted colors can beutilized for such applications. Then, the matrix with treated QDs iscoated over an LED and cured.

FIG. 7 is a graph depicting the performance of QDs before and after asurface treatment (at two different temperatures) with QDs depositeddirectly upon a blue light emitting LED. The QDs had a Cd_(x)Zn_(1-x)Secore and a ZnS shell, a particle size of around 6 nm, and were treatedwith zinc oleate in 1-octadecene. It can be seen that the treatmentsubstantially suppressed the photobrightening. For untreated QDs theemission increased by 18-19% from the original thermally equilibratedvalue after 80 minutes of constant illumination at approximately 200W/cm². The treatment at 150° C. partially suppressed thephotobrightening effect leading to an emission growth of approximately10%. Treatment at a lower temperature, such as 125° C., led tostabilized emission properties and a minimal change of intensity within5% upon extended irradiation. Instead of zinc, the QD nanocrystalsurfaces could have been treated using other divalent cations (e.g., Cd,Hg, or Pb) on the QD nanocrystal surfaces at similar temperatures.

In other aspects, the quantum dots may comprise a core and shell made,respectively, of cadmium and zinc chalcogenides, with a core size of 2-5nm and a shell thickness of 0-2 nm, and where the 1-100% of the surfaceatoms are exchanged with cadmium or zinc in such way that it results insuppressed photobrightening.

FIG. 8 is a flowchart illustrating a method for suppressing quantum dotphotobrightening. Although the method is depicted as a sequence ofnumbered steps for clarity, the numbering does not necessarily dictatethe order of the steps. It should be understood that some of these stepsmay be skipped, performed in parallel, repeated, or performed withoutthe requirement of maintaining a strict order of sequence. Generallyhowever, the method follows the numeric order of the depicted steps. Themethod starts at Step 800.

Step 802 provides QD nanocrystals having a surface, with a maximumcross-sectional dimension of 10 nm, capable of emissions in the visiblespectrum of light. In Step 804 the QD nanocrystal surfaces are treatedwith a solution including a multi-valent cation salt. In Step 806 thesolution is heated to a temperature in the range of 50 to 200 degrees C.In response to heating the solution, multi-valent cations becomeattached to the surface of the quantum dot nanocrystals in Step 808,forming treated QDs with suppressed photobrightening. In one aspect, themulti-valent cations become attached to the QD nanocrystal surfacesthrough pseudo-atomic layer deposition. Step 810 forms treated quantumdots emitting a non-varying intensity of first wavelength of light inthe visible spectrum when subjected to a continuous exposure of a secondwavelength of light having an intensity of greater than 50 W/cm².

In one aspect, forming the treated quantum dots emitting the non-varyingintensity of first wavelength of light in Step 810 includes the treatedQDs emitting a blue, green, or red color light when exposed to light inthe UV spectrum. In another aspect of Step 810, the treated QDs emit agreen or red color light when exposed to a blue color light.

Typically, Step 802 provides QD nanocrystals having either a solitarycore or core-single shell structure. In the case of a solitary core, thecore surface is the QD nanocrystal surface. In the case of a core-singleshell structure, the shell comprises the QD nanocrystal surface. If QDnanocrystal surface is a binary or binary alloyed material, then the QDnanocrystals are treated with a solution including divalent cation saltsin Step 804. For example, the QD surface may be: CdS, CdSe, CdTe, GaAs,InAs, InN, InP, ZnS, ZnSe, ZnTe, or combinations thereof. If Step 802provides QD nanocrystals with a surface that is a tertiary or tertiaryalloyed material, Step 804 treats the QD nanocrystals with trivalentcation salts, divalent cation salts, monovalent cation salts, orcombinations thereof. For example, the QD surface may be: ZnSSe, ZnSeTe,ZnSTe, CdSSe, CdSeTe, CdSTe, ZnCdS, ZnCdSe, ZnCdTe, ZnCdSSe, ZnCdSeTe,InGaAs, GaAlAs, InGaN, CuInS₂, CuGaS₂, Cu(In,Ga)Se₂, Cu(Zn,Sn)Se₂,Cu(Zn,Sn)S₂, Culn(Se,S)₂, CuZn(Se,S)₂, CuSn(Se,S)₂, Cu(Zn,Sn)(Se,S)₂, orcombinations thereof.

In one aspect, Step 802 provides QD nanocrystals with a surface that isa Type III-V semiconductor, and in Step 804 the QD surfaces are treatedwith a solution including trivalent cation salts, divalent cation salts,or combinations thereof. The trivalent cation salts may be comprised ofAl, Ga, In, Fe, Sb, or Bi.

FIG. 9 is a flowchart illustrating a method for forming a light emittingdiode device with suppressed quantum dot photobrightening. The methodstarts at Step 900. Step 902 provides QD nanocrystals having a surface,with a maximum cross-sectional dimension of 10 nm, capable of emissionsin the visible spectrum of light. In Step 904 the QD nanocrystalsurfaces are treated with a solution including a multi-valent cationsalt. In Step 906 the solution is heated to a temperature in the rangeof 50 to 200 degrees C. In response to heating the solution,multi-valent cations become attached to the surface of the quantum dotnanocrystals in Step 908, forming treated QDs with suppressedphotobrightening. In one aspect, the multi-valent cations becomeattached to the QD nanocrystal surfaces through pseudo-atomic layerdeposition. In Step 910 the treated QDs are deposited overlying a topsurface of an LED. Step 912 provides an LED device capable of emitting anon-varying intensity of a first wavelength light in the visiblespectrum from the treated QDs, when subjected to a continuous exposureof a second wavelength of LED light having an intensity of greater than50 W/cm². In one aspect, the treated QDs are mixed with an epoxy,silicon, or acrylate based polymer matrix materials in Step 909 to forma matrix paste, and the matrix paste is deposited on the LED in Step910.

For example, the LED device of Step 912 may include treated QDs emittinga non-varying intensity of blue, green, or red color light when exposedto LED light in the UV spectrum. In another example, the LED device ofStep 912 may include the treated QDs emitting a non-varying intensity ofgreen or red color light when exposed to a blue color LED light.

Typically, QD nanocrystals provided in Step 902 have either a solitarycore or core-single shell structure. In the case of a solitary core, thecore surface is the QD nanocrystal surface. In the case of a core-singleshell structure the shell comprises the QD nanocrystal surface. If theQD nanocrystals provided in Step 902 have a surface that is a binary orbinary alloyed material, then the QD nanocrystals are treated with asolution including divalent cation salts in Step 904. For example, theQD nanocrystal surface may be: CdS, CdSe, CdTe, GaAs, InAs, InN, InP,ZnS, ZnSe, ZnTe, or combinations thereof. If the QD nanocrystalsprovided in Step 902 have a surface that is a tertiary or tertiaryalloyed material, then in Step 904 the QD nanocrystals are treated withtrivalent cation salts, divalent cation salts, monovalent cation salts,or combinations thereof. For example, the QD nanocrystal surface may be:ZnSSe, ZnSeTe, ZnSTe, CdSSe, CdSeTe, CdSTe, ZnCdS, ZnCdSe, ZnCdTe,ZnCdSSe, ZnCdSeTe, InGaAs, GaAlAs, InGaN, CuInS₂, CuGaS₂, Cu(In,Ga)Se₂,Cu(Zn,Sn)Se₂, Cu(Zn,Sn)S₂, Culn(Se,S)₂, CuZn(Se,S)₂, CuSn(Se,S)₂,Cu(Zn,Sn)(Se,S)₂, or combinations thereof.

In one aspect, the QD nanocrystals provided in Step 902 have a surfacethat is a Type III-V semiconductor, and in Step 904 the QD nanocrystalsurfaces are treated with a solution including trivalent cation salts,divalent cation salts, or combinations thereof. Type III-Vsemiconductors are a group of binary semiconducting materials, where thecation is selected from Group III of the Periodic Table (e.g., Al, Ga,or In) and the anion is selected from the Group V (e.g., N, P, or As).The cation from Group III is trivalent, therefore the surface treatmentmay require trivalent cation for the treatment, but divalent cations arealso used. The trivalent cation salts may be comprised of Al, Ga, In,Fe, Sb, or Bi.

Treated quantum dots, QD LED devices, and associated fabricationprocesses have been presented for the suppression of the QDphotobrightening effect. Examples of particular hardware configurationsand process steps have been used to illustrate the invention. However,the invention is not limited to merely these examples. Other variationsand embodiments of the invention will occur to those skilled in the art.

We claim:
 1. A method for suppressing quantum dot photobrightening, themethod comprising: providing quantum dots (QD) nanocrystals having asurface with a maximum cross-sectional dimension of 10 nanometers (nm),capable of emissions with the visible spectrum of light; treating thequantum dot nanocrystal surface with a solution including a multi-valentcation salt; heating the solution to a temperature in a range of 50 to200 degrees C.; in response to heating the solution, attachingmulti-valent cations to the surface of the quantum dot nanocrystals;and, forming treated quantum dots with suppressed photobrightening,capable of emitting a non-varying intensity of first wavelength of lightin the visible spectrum when subjected to a continuous exposure of asecond wavelength of light having an intensity of greater than 50 wattsper square centimeter (W/cm²).
 2. The method of claim 1 whereinproviding the QD nanocrystals includes providing QD nanocrystals with astructure selected from the group consisting of a solitary core and acore-single shell structure.
 3. The method of claim 1 wherein providingthe QD nanocrystals includes providing QD nanocrystals comprising abinary or binary alloyed material surface; and, wherein treating the QDnanocrystals with the solution includes treating the QD nanocrystalsurfaces with a solution including a divalent cation salt.
 4. The methodof claim 3 wherein the QD nanocrystal surface is selected from the groupconsisting of CdS, CdSe, CdTe, GaAs, InAs, InN, InP, ZnS, ZnSe, ZnTe,and combinations thereof.
 5. The method of claim 1 wherein providing theQD nanocrystals includes providing QD nanocrystals with a tertiary ortertiary alloyed material surface; and, wherein treating the QDnanocrystals with the solution includes treating the QD nanocrystalsurfaces with a solution including a material selected from the groupconsisting of trivalent cation salts, divalent cation salts, monovalentcation salts, and combinations thereof.
 6. The method of claim 5 whereinthe QD nanocrystal surface is selected from the group consisting ofZnSSe, ZnSeTe, ZnSTe, CdSSe, CdSeTe, CdSTe, ZnCdS, ZnCdSe, ZnCdTe,ZnCdSSe, ZnCdSeTe, InGaAs, GaAlAs, InGaN, CuInS₂, CuGaS₂, Cu(In,Ga)Se₂,Cu(Zn,Sn)Se₂, Cu(Zn,Sn)S₂, Culn(Se,S)₂, CuZn(Se,S)₂, CuSn(Se,S)₂,Cu(Zn,Sn)(Se,S)₂, and combinations thereof.
 7. The method of claim 1wherein providing the QD nanocrystals includes providing QD nanocrystalshaving a Type III-V semiconductor surface; and, wherein treating the QDnanocrystals with the solution includes treating the QD nanocrystalsurfaces with a solution including a material selected from the groupconsisting of trivalent cation salts, divalent cation salts, andcombinations thereof.
 8. The method of claim 7 wherein the trivalentcation salts include a cation selected from the group consisting of Al,Ga, In, Fe, Sb, and Bi.
 9. The method of claim 1 wherein attachingmulti-valent cations to the surface of the quantum dot nanocrystalsurfaces includes the multi-valent cations becoming attached to the QDnanocrystal surfaces through pseudo-atomic layer deposition.
 10. Themethod of claim 1 wherein forming the treated quantum dots emitting thenon-varying intensity of first wavelength of light when subjected to acontinuous exposure of the second wavelength of light includes thetreated QDs emitting light selected from the group consisting of blue,green, and red color light when exposed to light in the ultraviolet (UV)spectrum.
 11. The method of claim 1 wherein forming the treated quantumdots emitting the non-varying intensity of first wavelength of lightwhen subjected to a continuous exposure of the second wavelength oflight includes the treated QDs emitting a light color selected from thegroup consisting of red and green when exposed to a blue color light.12. A method for forming a light emitting diode device with suppressedquantum dot photobrightening, the method comprising: providing quantumdot (QD) nanocrystals having a surface, with a maximum cross-sectionaldimension of 10 nanometers (nm), capable of emissions in the visiblespectrum of light; treating the quantum dot nanocrystal surfaces with asolution including a multi-valent cation salt; heating the solution to atemperature in a range of 50 to 200 degrees C.; in response to heatingthe solution, attaching multi-valent cations to the surface of thequantum dot nanocrystals to formed treated QDs with suppressedphotobrightening; depositing the treated QDs overlying a top surface ofa light emitting diode (LED); and, forming an LED device emitting anon-varying intensity of a first wavelength light in the visiblespectrum from the treated QDs when subjected to a continuous exposure ofa second wavelength of LED light having an intensity of greater than 50watts per square centimeter (W/cm²).
 13. The method of claim 12 whereinproviding the QD nanocrystals includes providing QD nanocrystals with astructure selected from the group consisting of a solitary core andcore-single shell structure.
 14. The method of claim 12 whereinproviding the QD nanocrystals includes providing QD nanocrystalscomprising a binary or binary alloyed material surface; and, whereintreating the QD nanocrystals with the solution includes treating the QDnanocrystal surface with a solution including divalent cation salts. 15.The method of claim 14 wherein the QD nanocrystal surface is selectedfrom the group consisting of CdS, CdSe, CdTe, GaAs, InAs, InN, InP, ZnS,ZnSe, ZnTe, and combinations thereof.
 16. The method of claim 12 whereinproviding the QD nanocrystal includes providing QD nanocrystals with atertiary or tertiary alloyed material surface; and, wherein treating theQD nanocrystals with the solution includes treating the QD nanocrystalsurfaces with a solution including a material selected from the groupconsisting of trivalent cation salts, divalent cation salts, monovalentcation salts, and combinations thereof.
 17. The method of claim 16wherein the QD nanocrystal surface is selected from the group consistingof ZnSSe, ZnSeTe, ZnSTe, CdSSe, CdSeTe, CdSTe, ZnCdS, ZnCdSe, ZnCdTe,ZnCdSSe, ZnCdSeTe, InGaAs, GaAlAs, InGaN, CuInS₂, CuGaS₂, Cu(In,Ga)Se₂,Cu(Zn,Sn)Se₂, Cu(Zn,Sn)S₂, CuIn(Se,S)₂, CuZn(Se,S)₂, CuSn(Se,S)₂,Cu(Zn,Sn)(Se,S)₂, and combinations thereof.
 18. The method of claim 12wherein providing the QD nanocrystals includes providing QD nanocrystalshaving a Type III-V semiconductor surface; and, wherein treating the QDnanocrystals with the solution includes treating the QD nanocrystalsurfaces with a solution including a material selected from the groupconsisting of trivalent cation salts, divalent cation salts, andcombinations thereof.
 19. The method of claim 18 wherein the trivalentcation salts include a material selected from the group consisting ofAl, Ga, In, Fe, Sb, and Bi.
 20. The method of claim 12 wherein attachingmulti-valent cations to the surface of the quantum dot nanocrystalsincludes the multi-valent cations becoming attached to the QDnanocrystal surfaces through pseudo-atomic layer deposition.
 21. Themethod of claim 12 further comprising: prior to depositing the treatedQDs overlying the top surface of the LED, mixing the treated QDs with amatrix material selected from the group consisting of epoxy, silicon,and acrylate based polymers to form a matrix paste; and, whereindepositing the treated QDs overlying the top surface of the LED includesdepositing the matrix paste.
 22. The method of claim 12 wherein formingthe LED device emitting the non-varying intensity of the firstwavelength light from the treated QDs when subjected to the continuousexposure of the second wavelength of LED light includes the treated QDsemitting a non-varying intensity of light selected from the groupconsisting of blue, green, and red color light when exposed to LED lightin the ultraviolet (UV) spectrum.
 23. The method of claim 12 whereinforming the LED device emitting the non-varying intensity of the firstwavelength light from the treated QDs when subjected to the continuousexposure of the second wavelength of LED light includes the treated QDsemitting a non-varying intensity of light color selected from the groupconsisting of red and green when exposed to a blue color LED light.24-44. (canceled)